The hydroboration of simple alkenes with BH3 preferentially occurs in an anti- Markovnikov fashion. The standard explanation for this preference, reproduced in all general organic chemistry textbooks, is that the selectivity arises from a greater stability for the anti-Markovnikov transition state. This explanation presupposes the applicability of the transition-state theory model for reactivity and selectivity. This dissertation explores the applicability of transition state theory to selectivity in hydroborations and finds that in some cases transition state theory fails to accurately account for observations. Experimental results for the hydroboration of propene-d6 and styrene-d8 with excess BH3 was analyzed by 2H-NMR to determine the percentage of the Markovnikov product for the BH3-mediated reaction. The experimental selectivities were then compared with predictions based on very high-level calculations using transition state theory. It was observed that the regioselectivity of the hydroboration of these alkenes is lower than can be accounted for by transition state theory. The regioselectivity discrepancy was explored through dynamic trajectory analysis. It is proposed here that the observed regioselectivity is that of a “hot” reaction, resulting from an exothermic association of alkene with borane to form an intermediate complex. This complex then overcomes low-energy barriers to form anti-Markovnikov and Markovnikov products faster than excess energy is lost to solvent. This hypothesis was explored for the hydroboration of internal disubstituted and trisubstituted alkenes. The applicability of transition state theory and the role of dynamics in determining the selectivity was gauged by determining product ratios in the presence of large excesses of borane and by considering the energetics of the calculated hydroboration reaction path. In all cases the enthalpic barriers for the rate-limiting association step and the formation of products from the intermediate π -complex were small. Isotope effects were determined experimentally and were found to be too small for the conventional mechanism to be the predominate pathway. When the hydroboration reaction of propene with BH2Cl or BHCl2 was explored through a series of experimental and theoretical studies, we observed that the regioselectivity was lower than that predicted from transition state theory. However, the calculated pathways indicated that energy barriers for product formation were too large for this reaction to be considered a “hot” reaction. The regioselectivity discrepancy was attributed to the chloroboranes undergoing equilibration with selective reaction of the most highly reactive forms of the borane.

À partir des années 1970 et notamment à travers les travaux de Tüxen (1978) puis de Géhu & Rivas-Martínez (1981), la phytosociologie dynamico-caténale a permis de mieux intégrer la dynamique des végétations en décrivant plus finement les trajectoires dynamiques des séries de végétation. Si les méthodologies d’étude des dynamiques des végétations se sont multipliées depuis les dernières décennies en Europe, de tels travaux restent peu nombreux en France. Un programme national de Cartographie des Habitats naturels et semi-naturels (CarHAB), lancé par le Ministère de l’Écologie, du Développement Durable et de l’Énergie, à partir de 2011, a pour objectif de cartographier les végétations et les séries de végétation de France métropolitaine à l’échelle du 1 : 25 000 d’ici 2025. Dans ce contexte, la Corse a été choisie comme région "pilote" pour les particularités de ses végétations méditerranéenne et alticole. Au-delà de cette singularité, l’évolution de la société agropastorale au cours du XXe siècle a profondément marqué le paysage végétal de Corse et constitue une des problématiques fondamentales permettant d’appréhender les changements des trajectoires dynamiques des végétations. La démarche méthodologique repose sur une méthode inductive et semi-déductive qui permet de décrire les systèmes de végétation de la Corse, à partir d’une approche phytosociologique. Notre étude, d’abord consacrée à l’approche bioclimatique, géomorphologique et phytogéographique, permet de typifier et de spatialiser les unités écologiques (géologie, géomorphologie, pédologie et bioclimatologie) afin de mieux appréhender les patrons écologiques qui régissent l’agencement et les zonations des végétations et plus largement les séries et les géoséries de végétation. Les fondements de la phytosociologie paysagère ont été révisés et adaptés aux objectifs de gestion conservatoire et d’aménagement du territoire, dans le cadre du programme CarHAB. 78 unités, soit 34 séries, 14 minoriséries et 30 géopermaséries sont décrites selon plusieurs critères : écologie, chorologie, structure et nomenclature de la tête de série, trajectoires dynamiques et conservation. Une méthode cartographique a été élaborée pour spatialiser les unités sigmétales et géosigmétales. L’ensemble des travaux cartographiques est présenté sous la forme d’un atlas cartographique concernant huit vallées et plateaux (Asco, Cap Corse, Niolu, Castagniccia, Haut-Vénacais, Plateau du Cuscione, Plateau calcaire de Bonifacio) et 31 sites littoraux.Quelques méthodes de bioévaluation sont testées et discutées, pour répondre aux enjeux de conservation des séries et des géoséries de végétation ainsi que de territoires protégés (étang de Biguglia, massif du Haut-Vénacais). / Since the 1970’s and particularly through the works of Tüxen (1978) and Géhu & Rivas-Martínez (1981), the dynamico-catenal phytosociology allowed to better integrate vegetation dynamics, by describing more precisely the dynamic trajectories of vegetation series. If vegetations dynamic study methodologies have been developped over the recent decades in Europe, such works still remain scarce in France. A national program of habitat mapping (CarHAB), launched by the Ministry of Ecology, since 2011, aims to map the vegetation and vegetation series of metropolitan France at the scale of 1: 25 000 up to 2025. Within this context, Corsica has been chosen as a "pilot" region, due to its peculiarities regarding mediterranean and alticole vegetations. Beyond this singularity, the evolution of agropastoral society over the twentieth century caused main changes the landscape of Corsica and represents a major issue to understand the changes of dynamic trajectories of vegetation. Our methodology, based on an inductive and semi-deductive phytosociological approach, allows to describe vegetationsystems of Corsica.This study, firstly focused on bioclimatology, geomorphology and phytogeography, allows to typify and spatialize ecological units, in order to better understand ecological patterns that govern the layout and the zonation of vegetation and more widely vegetation series and geoseries. The principles of landscape phytosociology have been revised and adapted to the conservation management aims and spatial planning of the CarHAB program. 78 units, 34 series, 14 minoriseries and 30 geopermaseries are presented according to several descriptive criteria: ecology, chorology, serie head structure and nomenclature, dynamics trajectories and conservation.A mapping method was developed to spatialize sigmetal and geosigmetal units : the outcomes are presented in a mapping atlas concerning eight valleys and trays (Asco, Cap Corse, Niolu, Fium-Alto, Haut-Vénacais, Cuscione, Bonifacio) and 31 coastal sites.A few bioevaluation methods are tested and discussed to match the challenges of conservation series and vegetation géoséries, as well as evaluation protected sites (Biguglia, Haut-Vénacais).